Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III)
The study of inorganic crystalline materials by solid-state NMR spectroscopy is often complicated by the low sensitivity of heavy nuclei. However, these materials often contain or can be prepared with paramagnetic dopants without significantly affecting the structure of the crystalline host. Dynamic...
| Main Authors: | , , , , , , |
|---|---|
| Other Authors: | |
| Format: | Article |
| Language: | en_US |
| Published: |
American Chemical Society (ACS)
2017
|
| Online Access: | http://hdl.handle.net/1721.1/110494 https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0003-1589-832X |
| _version_ | 1826203171222978560 |
|---|---|
| author | Luchinat, Claudio Corzilius, Bjorn Michaelis, Vladimir K. Penzel, Susanne Ravera, Enrico Griffin, Robert Guy Smith, Albert A. |
| author2 | Massachusetts Institute of Technology. Department of Chemistry |
| author_facet | Massachusetts Institute of Technology. Department of Chemistry Luchinat, Claudio Corzilius, Bjorn Michaelis, Vladimir K. Penzel, Susanne Ravera, Enrico Griffin, Robert Guy Smith, Albert A. |
| author_sort | Luchinat, Claudio |
| collection | MIT |
| description | The study of inorganic crystalline materials by solid-state NMR spectroscopy is often complicated by the low sensitivity of heavy nuclei. However, these materials often contain or can be prepared with paramagnetic dopants without significantly affecting the structure of the crystalline host. Dynamic nuclear polarization (DNP) is generally capable of enhancing NMR signals by transferring the magnetization of unpaired electrons to the nuclei. Therefore, the NMR sensitivity in these paramagnetically doped crystals might be increased by DNP. In this paper we demonstrate the possibility of efficient DNP transfer in polycrystalline samples of [Co(en)[subscript 3]Cl[subscript 3]][subscript 2]·NaCl·6H[subscript 2]O (en = ethylenediamine, C[subscript 2]H[subscript 8]N[subscript 2]) doped with Cr(III) in varying concentrations between 0.1 and 3 mol %. We demonstrate that [superscript 1]H, [superscript 13]C, and [superscript 59]Co can be polarized by irradiation of Cr(III) with 140 GHz microwaves at a magnetic field of 5 T. We further explain our findings on the basis of electron paramagnetic resonance spectroscopy of the Cr(III) site and analysis of its temperature-dependent zero-field splitting, as well as the dependence of the DNP enhancement factor on the external magnetic field and microwave power. This first demonstration of DNP transfer from one paramagnetic metal ion to its diamagnetic host metal ion will pave the way for future applications of DNP in paramagnetically doped materials or metalloproteins. |
| first_indexed | 2024-09-23T12:32:28Z |
| format | Article |
| id | mit-1721.1/110494 |
| institution | Massachusetts Institute of Technology |
| language | en_US |
| last_indexed | 2024-09-23T12:32:28Z |
| publishDate | 2017 |
| publisher | American Chemical Society (ACS) |
| record_format | dspace |
| spelling | mit-1721.1/1104942022-09-28T08:26:43Z Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) Dynamic Nuclear Polarization of 1H, 13C, and 59Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) Luchinat, Claudio Corzilius, Bjorn Michaelis, Vladimir K. Penzel, Susanne Ravera, Enrico Griffin, Robert Guy Smith, Albert A. Massachusetts Institute of Technology. Department of Chemistry Francis Bitter Magnet Laboratory (Massachusetts Institute of Technology) Corzilius, Bjorn Michaelis, Vladimir K. Penzel, Susanne Ravera, Enrico Smith, Albert Andrew Griffin, Robert Guy The study of inorganic crystalline materials by solid-state NMR spectroscopy is often complicated by the low sensitivity of heavy nuclei. However, these materials often contain or can be prepared with paramagnetic dopants without significantly affecting the structure of the crystalline host. Dynamic nuclear polarization (DNP) is generally capable of enhancing NMR signals by transferring the magnetization of unpaired electrons to the nuclei. Therefore, the NMR sensitivity in these paramagnetically doped crystals might be increased by DNP. In this paper we demonstrate the possibility of efficient DNP transfer in polycrystalline samples of [Co(en)[subscript 3]Cl[subscript 3]][subscript 2]·NaCl·6H[subscript 2]O (en = ethylenediamine, C[subscript 2]H[subscript 8]N[subscript 2]) doped with Cr(III) in varying concentrations between 0.1 and 3 mol %. We demonstrate that [superscript 1]H, [superscript 13]C, and [superscript 59]Co can be polarized by irradiation of Cr(III) with 140 GHz microwaves at a magnetic field of 5 T. We further explain our findings on the basis of electron paramagnetic resonance spectroscopy of the Cr(III) site and analysis of its temperature-dependent zero-field splitting, as well as the dependence of the DNP enhancement factor on the external magnetic field and microwave power. This first demonstration of DNP transfer from one paramagnetic metal ion to its diamagnetic host metal ion will pave the way for future applications of DNP in paramagnetically doped materials or metalloproteins. National Institutes of Health (U.S.) (EB00280) National Institutes of Health (U.S.) (EB002026) German Science Foundation (DFG Research Fellowship CO 802/1-1) Natural Sciences and Engineering Research Council of Canada (Banting Postdoctoral Fellowship) European Molecular Biology Organization (ASTF-491/2013) 2017-07-06T17:34:23Z 2017-07-06T17:34:23Z 2014-07 2014-05 Article http://purl.org/eprint/type/JournalArticle 0002-7863 1520-5126 http://hdl.handle.net/1721.1/110494 Corzilius, Björn et al. “Dynamic Nuclear Polarization of 1 H, 13 C, and 59 Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III).” Journal of the American Chemical Society 136.33 (2014): 11716–11727. © 2014 American Chemical Society https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0003-1589-832X en_US http://dx.doi.org/10.1021/ja5044374 Journal of the American Chemical Society Article is made available in accordance with the publisher's policy and may be subject to US copyright law. Please refer to the publisher's site for terms of use. application/pdf American Chemical Society (ACS) ACS |
| spellingShingle | Luchinat, Claudio Corzilius, Bjorn Michaelis, Vladimir K. Penzel, Susanne Ravera, Enrico Griffin, Robert Guy Smith, Albert A. Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title | Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title_full | Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title_fullStr | Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title_full_unstemmed | Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title_short | Dynamic Nuclear Polarization of [superscript 1]H, [superscript 13]C, and [superscript 59]Co in a Tris(ethylenediamine)cobalt(III) Crystalline Lattice Doped with Cr(III) |
| title_sort | dynamic nuclear polarization of superscript 1 h superscript 13 c and superscript 59 co in a tris ethylenediamine cobalt iii crystalline lattice doped with cr iii |
| url | http://hdl.handle.net/1721.1/110494 https://orcid.org/0000-0002-6708-7660 https://orcid.org/0000-0003-1589-832X |
| work_keys_str_mv | AT luchinatclaudio dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT corziliusbjorn dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT michaelisvladimirk dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT penzelsusanne dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT raveraenrico dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT griffinrobertguy dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT smithalberta dynamicnuclearpolarizationofsuperscript1hsuperscript13candsuperscript59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT luchinatclaudio dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT corziliusbjorn dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT michaelisvladimirk dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT penzelsusanne dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT raveraenrico dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT griffinrobertguy dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii AT smithalberta dynamicnuclearpolarizationof1h13cand59coinatrisethylenediaminecobaltiiicrystallinelatticedopedwithcriii |